丙烯醛水合加氢制1，3—丙二醇

考察了丙烯醛水合及3-羟基丙醛加氢制1，3-丙二醇的工艺条件。在装有阳离子交换树脂催化剂的固定床层反应中，当水合温度40～55℃，空速3～5h^-1、丙烯醛质量分数13%～17%，并加入少量对苯二酚阻聚剂时，丙烯醛单程转化率可达到85%，选择性大于90%，在高压釜内进行3-羟基丙醛加氢时，催化剂投料量1.5%～2.0%，一段加氢温度30～50℃，二段加氢温度110～130℃，氢气压力6.0MPa，搅拌速度500r/min，使用细颗粒Raney镍催化剂，可使3-羟基丙醛加氢转化率达到100%，1，3-丙二醇的选择性也在99%以上，在产品中醛基含量小于300μg/g。     

Reaction pathways for the oxygenates formation from propane and oxygen over potassium‐modified Fe/SiO2 catalysts

The partial oxidation of propane has been compared on Fe/SiO₂ and alkali‐modified Fe/SiO₂ catalysts. Addition of K⁺ to the catalyst can appreciably enhance the conversion of propane along with a high selectivity toward oxygenates. Adjacency of Fe and K on the silica surface seems to be important for the high oxygenate yield. Through the study on the reaction pathways, two types of intermediates, one derived from propene and the other from propan‐2‐ol, were postulated. The former is related to the acrolein formation and the latter to the acetone formation. Contribution of alkali‐catalyzed aldol condensation is also discussed for the formation of oxygenates with higher carbon numbers. This revised version was published online in July 2006 with corrections to the Cover Date.     

乙炔羰基合成的研究进展

对乙炔碳基合成丙烯酸(酯)、丁二酸酸酐、丁烯二酸二丁酯和丙烯醛等系列有机产品进行了综述。重点探讨了乙炔碳基合成丙烯酸(酯)的催化剂和反应工艺条件。镍基和钯基催化剂是催化乙炔羰基合成丙烯酸(酯)的良好催化剂,同时钯基催化剂也是催化乙炔羰基合成丁二酸酸酐和丁烯酸二酯的良好催化剂。镍聚和钯基催化剂的复合及负载化是今后乙炔羰基合成研究的主要发展方向。     

Genesis of site isolation and phase cooperation in selective oxidation catalysis

Two of the important principles governing selective oxidation catalysis are site isolation and phase cooperation. They are discussed here in light of their inception, development, historic perspective and current acceptance in the field of selective oxidation and ammoxidation catalysis.     

Fundamental Principles of Selective Heterogeneous Oxidation Catalysis

Seven principles (seven pillars) underpinning selective heterogeneous oxidation catalysis, comprising lattice oxygen, metal-oxygen bond strength, host structure, redox, multifunctionality of active sites, site isolation, and phase cooperation are described. Their intended utilization towards a deeper understanding of metal oxide catalyst behavior and application towards catalyst design are indicated.     

磷酸锆负载金属氧化物催化剂的制备及其在甘油脱水制丙烯醛中的应用

以磷酸锆为载体,负载不同类型金属氧化物制备了系列MOx/ZrP催化剂,即FeO_x/ZrP、CoO_x/ZrP、NiO_x/ZrP、NbO_x/ZrP、CuO_x/ZrP、MoO_x/ZrP和WOx/ZrP,并采用XRD、FT-IR、SEM、EDS、TEM、NH3-TPD和N2吸附-脱附等对催化剂进行表征,结果表明,金属氧化物的负载对磷酸锆载体的微观形貌、孔结构以及酸性质等均产生了显著影响。将MOx/ZrP催化剂用于甘油脱水制丙烯醛反应,结果表明,金属负载质量分数为5%的WO_x/ZrP催化剂反应效果最好,甘油转化率达93%,且丙烯醛选择性为82%。     

四苯基铁卟啉仿生催化丙烯环氧化合成环氧丙烷的研究

合成了四苯基铁卟啉并用于催化丙烯环氧化合成环氧丙烷,考察了共还原剂种类、催化剂浓度、共还原剂用量、反应时间、反应温度、反应压力对实验的影响。该反应适宜的条件为1.74×10~(-5)mol/L催化剂TPPFe~(Ⅲ)Cl;1.31×10~(-4)mol/L助催化剂3-吲哚乙酸;共还原剂丙烯醛,n(正丁醛)∶n(丙烯)=1∶1.2;溶剂二氯甲烷,n(二氯甲烷)∶n(丙烯)=15.45;反应温度98℃;反应压力1.65 MPa;反应时间1.8 h。在该条件下,丙烯的转化率为35.04%,环氧丙烷的收率和选择性分别达34.28%和97.83%。     

丙烯醛水合液化学分析方法的研究

丙烯醛水合反应液中主要含有产物和丙烯醛，本文用化学分析方法检测出未反应的丙烯醛，得出反应的转化率来监测反应。     

3-羟基丙醛加氢制1,3-丙二醇的研究

以Ni／Al2O3为催化剂，在固定床反应器上考察了3-羟基丙醛(3-HPA)加氢制1，3-丙二醇(1，3-PDO)的反应工艺条件，结果表明，当反应温度为70℃、反应压力为5．0MPa、氢气与3-羟基丙醛摩尔比为7．0,3-HPA液时空速(IHSV)为6．0h^-1时，3．HPA转化率100％，1，3-PDO选择性大于99％。